Cumulative potential and half-life of [imazapic + imazapyr] in lowland soils of Rio Grande Do Sul grown with clearfield® rice.

The objectives of this study were to estimate the residual and half-life of [imazapic + imazapyr] and to infer on the impact of these residuals over time. The first experiment comprised the application of [imazapic + imazapyr] to Clearfield® rice. On the following summer cropping season (365 days later), undeformed soil samples 0-5 cm depth were collected and seeds of six species or varieties were sown as bioindicators of residuals (experiment 2), being assessed plant height and dry mass 20 days after emergence start. The third experiment comprised the cultivation of the same species submitted to ten increasing herbicide doses (0-280 g ha-1) to establish standard response curves, also assessing plant height and dry mass 20 days after emergence start. About 2.1-5.8% of the applied imazapic remains in soil after one year, for the label doses. Imazapyr was considered to be at negligible doses as its half-life is short, and less than 0.0000001% of the applied dose is expected to be in soil 365 days later. The expected imazapic half-life in lowland areas of Southern Brazil is longer than for dryland, being estimated as between 63 and 77 days (95% confidence interval), contrasting to the 60 days half-life previously estimated for dryland soils.

Determination of paraquat and diquat: LC-MS method optimization and validation.

This study describes the optimization and single-laboratory validation of a single residue method for determination of two bipyridylium herbicides, paraquat and diquat, in cowpeas by UPLC-MS/MS in a total run time of 9.3min. The method is based on extraction with an acidified methanol-water mixture. Different extraction parameters (extraction solvent composition, temperature, sample extract filtration, and pre-treatment of the laboratory sample) were evaluated in order to optimize the extraction method efficiency. Isotopically labeled internal standards, Paraquat-D6 and Diquat-D4, were used and added to the test portions prior to extraction. The method validation was performed by analyzing spiked samples at three concentrations (10, 20 and 50µgkg(-1)), with seven replicates (n=7) for each concentration. Linearity (r(2)) of analytical curves, accuracy (trueness as recovery % and precision as RSD%), instrument and method limits of detection and quantification (LOD and LOQ) and matrix effects were determined. Average recoveries obtained for diquat were between 77 and 85% with RSD values ⩽20%, for all spike levels studied. On the other hand, paraquat showed average recoveries between 68 and 103% with RSDs in the range 14.4-25.4%. The method LOQ was 10 and 20µgkg(-1) for diquat and paraquat, respectively. The matrix effect was significant for both pesticides. Consequently, matrix-matched calibration standards and using isotopically labeled (IL) analogues as internal standards for the target analytes are required for application in routine analysis. The validated method was successfully applied for cowpea samples obtained from various field studies.